Process for purifying exhaust gases

Abstract: A catalyst for purifying exhaust gases includes a porous support, at least one catalyst ingredient selected from Pt and Pd, and additional ingredients including (1) at least two rare-earth elements including La, (2) at least one rare-earth element including La and at least one transition element selected from Fe, Ni, Co and Mn, (3) at least two alkali metals, (4) at least one alkali metal and at least one rare-earth element including La, (5) at least one alkali metal and at least one transition element selected from Fe, Ni, Co and Mn, (6) at least two alkaline-earth metals, (7) at least one alkaline-earth metal and at least one rare-earth element including La, or (8) Ba, Li, La, Ce and Zr. A process for purifying an exhaust gas, by contacting the catalyst with an exhaust gas, is also provided.

Description: BACKGROUND OF THE INVENTION Field of the Invention The present invention relates to a process for purifying exhaust gases. More particularly, it relates to a process which can efficiently purify nitrogen oxides (NO x ) in the exhaust gases which contain oxygen in excessive amounts required for oxidizing carbon monoxide (CO) and hydrocarbons (HC) therein. Description of Related Art As catalysts for purifying automotive exhaust gases, there have been employed 3-way catalysts so far which oxidize CO and HC and reduces NO x simultaneously to purify the exhaust gases. For example, the 3-way catalysts have been known widely which comprise a heat resistant support formed of cordierite, a catalyst carrier layer formed of gamma-alumina and disposed on the support, and a noble metal selected from the group consisting of Pt, Pd and Rh and loaded on the catalyst carrier layer. The purifying performance of the 3-way catalysts for purifying exhaust gases depends on the air-fuel ratio (A/F) of automotive engine. For instance, when the air-fuel ratio is large, i.e., when the fuel concentration is small (or on the fuel-lean side), the oxygen concentration is large. Accordingly, the oxidation reactions purifying CO and HC are active, but the reduction reactions purifying NO x are inactive. On the other hand, when the air-fuel ratio is small, i.e., when the fuel concentration is more (or on the fuel-rich side), the oxygen concentration is small. Accordingly, the oxidation reactions are inactive, but the reduction reactions are active. Moreover, when driving automobiles, especially when driving automobiles in urban areas, the automobiles are accelerated and decelerated frequently. Consequently, the air-fuel ratio varies frequently in the range of from the values adjacent to the stoichiometric point (or the ideal air-fuel ratio) to the fuel-rich side. In order to satisfy the low fuel consumption requirement during the driving in urban areas, it is necessary to operate the automobiles on the fuel-lean side where the air-fuel mixture containing oxygen as excessive as possible is supplied to the engines. Hence, it has been desired to develop a catalyst which is capable of adequately purifying NO x on the fuel-lean side (i.e., in the oxygen-rich atmospheres). Under the circumstances, as set forth in JP-A-5-168860, the applicants of the present invention disclosed a catalyst with rare-earth elements including La, and Pt loaded. With the catalyst, NO x is absorbed on the rare-earth elements during the the fuel-lean side (i.e., in the oxygen-rich atmospheres) driving, and it is purified by reacting with the reducing gases such as HC and the like, when the automobiles are driven under the air-fuel ratios at the stoichiometric point or on the fuel-rich side (i.e., in the oxygen-lean atmospheres). Thus, the catalyst is superb in the purifying performance of NO x even on the fuel-lean side (i.e., in the oxygen-rich atmospheres). The catalyst is believed to provide the advantageous effect because the rare-earth elements are loaded on the support in a form of the simple oxides and the simple oxides of the rare-earth elements and they react with NO x so as to produce the nitrates thereof. However, the exhaust gases usually contain SO 2 which are produced by burning sulfur (S) contained in the fuel. Further, the catalyst ingredient oxidizes SO 2 to SO 3 in the oxygen-rich atmospheres (i.e., on the fuel-lean side). Then, SO 3 reacts readily with water contained in the exhaust gases to produce sulfuric acid. The sulfate ions or the sulfite ions react with rare-earth elements to produce the sulfates or the sulfites incapable of absorbing NO x . Accordingly, the catalyst is not completely satisfactory in terms of the NO x purifying performance and the durability of the performance at elevated temperatures. DE-A-40 08 371 discloses an exhaust gas purification catalyst comprising a noble metal catalyst (base metal catalyst) and a metal catalyst (alkali metal catalyst) containing at least an alkali metal element and one or more elements selected from transition metal elements (except for elements of the platinum group) and Sn. The base metal catalyst is provided with low density and the alkali metal catalyst is provided with high density on different regions of the porous support. SUMMARY OF THE INVENTION The present invention has been developed in view of the aforementioned circumstances. It is therefore an object of the present invention to efficiently purify NO x in exhaust gases containing oxygen in excessive amounts and improve the catalyst in terms of the durability of the NO x purifying performance at elevated temperatures. In accordance with the present invention, a catalyst or a process comes to be able to carry out the above object, and they can simultaneously purify carbon monoxide, hydrocarbons and nitrogen oxides in exhaust gases in oxygen-rich atmospheres, thereby purifying the exhaust gases. It is one of the features of the present invention that novel and specific ingredients are loaded on the catalyst for purifying exhaust gases which is brought into contact with the exhaust gases containing oxygen in excessive amounts. Unless otherwise specified, the loading amounts of the catalyst ingredient or the following ingredients mean the amounts thereof loaded on a unit volume of a porous support and expressed in grams or moles with respect the unit volume (e.g., 1 liter). First of all, at least one catalyst ingredient selected from the group consisting of platinum (Pt) and palladium (Pd) is loaded on a catalyst according to the present. It is preferred to load rhodium (Rh) thereon in addition to Pt and Pd. The loading amount of the catalyst ingredient can preferably fall in a range of from 0.1 to 10 grams/liter when one of the catalyst ingredients are loaded thereon independently, and it can preferably fall in a range of from 0.1 to 10 grams/liter in total when they are combined and loaded thereon. The loading amount can further preferably fall in a range of 0.5 to 3.0 grams/liter. In a first aspect of the present invention, a catalyst used according to the present invention comprises, in addition to the above-described catalyst ingredients, at least two ingredients loaded thereon. The ingredients are selected from the group consisting of alkali metals, and they can preferably be K, Li, Na, Rb and Cs. The loading amounts of the two ingredients (or the two alkali metal ingredients) can preferably fall in a range of from 0.05 to 2.0 moles/liter in total. When the ingredients are loaded in an amount of less than the lower limit, the durability of the NO x purifying performance deteriorates at elevated temperatures. When the ingredients are loaded in an amount more than the upper limit, the advantageous effects resulting from the loading saturate, and the porous support diminishes the surface area. Hence, it is unpreferable to load the ingredients in such loading amounts deviating from the range. In a second aspect of the present invention, a catalyst used according to the present invention comprises, in addition to the above-described catalyst ingredients, at least one first ingredient loaded thereon, and at least one second ingredient loaded thereon. The first ingredient is selected from the group consisting of alkali metals. The second ingredient is selected from the group consisting of rare-earth elements including La. The alkali metals can preferably be K, Li, Na, Rb and Cs. The rare-earth elements including La can preferably be lanthanides such as La, Pr, Nd and Sm. The loading amount of the first ingredient (or the alkali metal ingredient) can preferably fall in a range of from 0.05 to 1.0 mole/liter. The loading amount of the second ingredient (or the rare-earth element ingredient) can preferably fall in a range of from 0.05 to 1.0 mole/liter. The loading amount of the first ingredient and the loading amount of the second ingredient can preferably fall in a range of from 0.1 to 2.0 moles/liter in total. When the first ingredient and the second ingredient are loaded in an amount of less than the lower limit, the durability of the NO x purifying performance deteriorates at elevated temperatures. When the first ingredient and the second ingredient are loaded in an amount more than the upper limit, the advantageous effects resulting from the loading saturate, and the porous support diminishes the surface area. Hence, it is unpreferable to load the first ingredient and the second ingredient in such loading amounts deviating from the range. In a third aspect of the present invention, a catalyst used according to the present invention comprises, in addition to the above-described catalyst ingredients, at least one first ingredient loaded thereon, and at least one second ingredient loaded thereon. The first ingredient is selected from the group consisting of alkali metals, and it can preferably be K, Li, Na, Rb and Cs. The second ingredient is selected from the group consisting of transition elements, selected from be Fe, Ni, Co and Mn. The loading amount of the first ingredient (or the alkali metal ingredient) can preferably fall in a range of from 0.05 to 1.0 mole/liter. The loading amount of the second ingredient (or the transition element ingredient) can preferably fall in a range of from 0.05 to 1.0 mole/liter. The loading amount of the first ingredient and the loading amount of the second ingredient can preferably fall in a range of from 0.1 to 2.0 moles/liter in total. When the first ingredient and the second ingredient are loaded in an amount of less than the lower limit, the durability of the NO x purifying performance deteriorates at elevated temperatures. When the first ingredient and the second ingredient are loaded in an amount more than the upper limit, the advantageous effects resulting from the loading saturate, and the porous support diminishes the surface area. Hence, it is unpreferable to load the first ingredient and the second ingredient in such loading amounts deviating from the range. In a fourth of the present invention, a catalyst used according to the present invention comprises, in addition to the above-described catalyst ingredients, at least two ingredients loaded thereon. The two ingredients are selected from the group consisting of alkaline-earth metals, and they can preferably be Mg, Ca, Ba and Sr. The loading amount of each of the two ingredients (or the two alkaline-earth metal ingredients) can preferably fall in a range of from 0.05 to 1.0 mole/liter, and the loading amounts of the two ingredients can preferably fall in a range of from 0.1 to 2.0 moles/liter in total. When the ingredients are loaded in an amount of less than the lower limit, the durability of the NO x purifying performance deteriorates at elevated temperatures. When the ingredients are loaded in an amount more than the upper limit, the advantageous effects resulting from the loading saturate, and the porous support diminishes the surface area. Hence, it is unpreferable to load the ingredients in such loading amounts deviating from the range. In a fifth aspect of the present invention, a catalyst used according to the present invention comprises, in addition to the above-described catalyst ingredients, at least one first ingredient loaded thereon, and at least one second ingredient loaded thereon. The first ingredient is selected from the group consisting of alkaline-earth metals, and it can preferably be Mg, Ca, Ba and Sr. The second ingredient is selected from the group consisting of rare-earth elements including La, and it can preferably be one of lanthanides such as La, Pr, Nd and Sm. The loading amount of the first ingredient (or the alkaline-earth metal ingredient) can preferably fall in a range of from 0.05 to 1.0 mole/liter. The loading amount of the second ingredient (or the rare-earth element ingredient) can preferably fall in a range of from 0.05 to 1.0 mole/liter. The loading amount of the first ingredient and the loading amount of the second ingredient can preferably fall in a range of from 0.1 to 2.0 moles/liter in total. When the first ingredient and the second ingredient are loaded in an amount of less than the lower limit, the durability of the NO x purifying performance deteriorates at elevated temperatures. When the first ingredient and the second ingredient are loaded in an amount more than the upper limit, the advantageous effects resulting from the loading saturate, and the porous support diminishes the surface area. Hence, it is unpreferable to load the first ingredient and the second ingredient in such loading amounts deviating from the range. As to a material for constituting the porous support, it can, for example, be alumina, zeolite, zirconia, silica alumina, silica, or the like. These materials can be formed into the porous support, or they can be coated on a honeycomb support formed of cordierite, heat resistant metal, or the like. In accordance with a process of the present invention for purifying exhaust gases, either one of the five present catalysts is brought into contact with oxygen-rich exhaust gases, whose oxygen concentrations are the stoichiometric point or more required for oxidizing the components to be oxidized therein, thereby purifying the exhaust gases, whereby the inventive process comprises the steps as defined in claims 1 to 5, respectively. In the first aspect of the present invention, the present catalyst comprises at least two ingredients selected form the group consisting of alkali metals and loaded compositely on the porous support. The two ingredients retrieve SO 2 contained in the exhaust gases into the present catalyst in a form of composite sulfates. In the second aspect of the present invention, the present catalyst comprises at least one first ingredient selected from the group consisting of alkali metals, and at least one second ingredient selected from the group consisting of rare-earth elements including La. The first and second ingredients are loaded compositely on the porous support, and they retrieve SO 2 contained in the exhaust gases into the present catalyst in a form of composite sulfates. In the third aspect of the present invention, the present catalyst comprises at least one first ingredient selected from the group consisting of alkali metals, and at least one second ingredient selected from the group consisting of Fe, Ni, Co, and Mn. The first and second ingredients are loaded compositely on the porous support, and they retrieve SO 2 contained in the exhaust gases into the present catalyst in a form of composite sulfates. In the fourth aspect of the present invention, the present catalyst comprises at least two ingredients selected form the group consisting of alkaline-earth metals and loaded compositely on the porous support. The two ingredients retrieve SO 2 contained in the exhaust gases into the present catalyst in a form of composite sulfates. In the fifth aspect of the present invention, the present catalyst comprises at least one first ingredient selected from the group consisting of alkaline-earth metals, and at least one second ingredient selected from the group consisting of rare-earth elements including La. The first and second ingredients are loaded compositely on the porous support, and they retrieve SO 2 contained in the exhaust gases into the present catalyst in a form of composite sulfates. In the process for purifying exhaust gases according to the present invention, either one of the five present catalysts is brought into contact with the oxygen-rich exhaust gases. Hence, SO 2 contained in the exhaust gases is retrieved by the action of the ingredients into the present catalysts in a form of composite sulfates. The resulting composite sulfates are more likely to decompose at low temperatures in the atmospheres ranging from the stoichiometric atmosphere to the fuel-rich atmospheres (i.e., in the oxygen-lean atmospheres) than the simple sulfates resulting from the independent ingredients. As a result, the rare-earth element ingredients including La, the alkali metal ingredients and the alkaline-earth metal ingredients can reproduce their NO x storage abilities because the composite sulfates are likely to decompose and release SO 2 . Thus, in the fuel-lean atmospheres (i.e., in the oxygen-rich atmospheres), NO x is absorbed or stored in the present catalyst for purifying exhaust gases. Then, in atmospheres ranging from the stoichiometric atmosphere to the fuel-rich atmospheres (i.e., in the oxygen-lean atmospheres), NO x is reacted with CO and HC contained in the exhaust gases, and it is reduced to N 2 . Namely, in the atmospheres ranging from stoichiometric atmosphere to the fuel-rich atmospheres (i.e., in the oxygen-lean atmospheres), NO x is reduced and purified, and at the same time CO and HC are oxidized and purified as well. With the above-described mechanism, it is believed that the present catalyst for purifying exhaust gases can maintain the NO x absorbing ability for a long period of time, and accordingly it can keep the catalyst activity high. In addition, when at least two of the alkali metal ingredients and the alkaline-earth metal ingredients are loaded compositely, they come to have smaller particle diameters, and they hardly grow to the crystalline sulfates because the composite sulfates are likely to decompose and release SO 2 . As a result, they can be kept to be highly dispersed for a long period of time, they can produce large surface areas capable of contacting NO x , and they can be disposed close to Pt and/or Pd so as to facilitate the catalyst reaction. Hence, the composite loading is believed to be one of the reasons why the present catalyst can keep the high catalyst activity even after it is subjected to a harsh durability test. As having been described so far, in accordance with the present catalyst for purifying exhaust gases or the present process therefor, superb NO x purifying performance can be maintained even after a durability test is carried out, and NO x can be purified efficiently even in the atmospheres on the fuel-lean side where the exhaust gases contain oxygen in excessive amounts. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Having generally described the present invention, a further understanding can be obtained by reference to the specific preferred embodiments which are provided herein for purposes of illustration only and are not intended to limit the scope of the appended claims. Unless otherwise specified, a term, "parts," hereinafter means "parts by weight." Reference Embodiment* 100 parts of an alumina powder, 70 parts of alumina sol containing alumina in an amount of 10% by weight, 15 parts of an aqueous aluminum nitrate solution containing aluminum nitrate in an amount of 40% by weight, and 30 parts of water were mixed, thereby preparing a slurry for coating. Then, a plurality of honeycomb supports formed of cordierite were immersed into the slurry, and thereafter each of them was blown to blow away the slurry in excess. After drying, each of the supports was burned at 600 °C for 1 hour, thereby forming an alumina coating layer thereon. The alumina coating layer was thus coated on the support in an amount of 120 grams with respect to 1 liter of the support. Each of the honeycomb supports with the alumina coating layer formed thereon was immersed into an aqueous platinum dinitrodiammine solution or an aqueous palladium nitrate solution, and thereafter it was blown to blow away the water droplets in excess. After the blowing, each of the supports was dried at 250 °C for 3 hours, thereby loading Pt or Pd thereon. The loading amounts of Pt or Pd are set forth in Table 1 below. Finally, each of the honeycomb supports with Pt or Pd loaded was immersed into a mixed aqueous solution which contains nitrates of rare-earth elements including La in predetermined concentrations. The term, "rare-earth elements," hereinafter means "rare-earth elements including La." The rare-earth elements employed were La, Pr, Nd and Sm. Each of the mixed aqueous solutions was prepared by mixing the nitrates of rare-earth elements with water so as to load the rare-earth element ingredients in loading amounts set forth in Table 1 below. Each of the supports was then blown to blow away the water droplets in excess. After drying, each of the supports was burned at 600 °C for 1 hour, thereby completing each of the present catalysts designated at No. 1 through No. 9 in Table 1. Reference Embodiment II Reference Embodiment II, e.g. catalysts designated at No. 22 through No. 29 in Table 1 below, were prepared in the same manner as described in the "Reference Embodiment I" section except that each of the honeycomb supports with Pt or Pd loaded was immersed into an aqueous solution which contains one and only nitrate of rare-earth elements, thereby loading one and only rare-earth element ingredient thereon. First Preferred Embodiments A plurality of honeycomb supports were prepared by coating them with the alumina coating layer in the same manner as described in the "Reference Embodiment I" section. Each of the honeycomb supports with the alumina coating layer formed thereon was immersed into an aqueous platinum dinitrodiammine solution or an aqueous palladium nitrate solution, and thereafter it was blown to blow away the water droplets in excess. After the blowing, each of the supports was dried at 250 °C for 3 hours, thereby loading Pt or Pd thereon. The loading amounts of Pt or Pd are set forth in Table 2 below. Then, each of the supports with Pt or Pd loaded was immersed into a mixed aqueous solution which contains nitrates of alkali metals in predetermined concentrations. Each of the mixed aqueous solutions was prepared by mixing the nitrates of alkali metals with water so as to load the alkali metal ingredients in loading amounts set forth in Table 2 below. The alkali metals employed were Li, Na, K, Rb and Cs. Each of the supports was then blown to blow away the water droplets in excess. After drying, each of the supports was burned at 600 °C for 1 hour, thereby completing each of the present catalysts designated at No. 30 through No. 41 in Table 2. Second Preferred Embodiments A plurality of honeycomb supports with Pt loaded were prepared in the same manner as described in the "Reference Embodiment I" section. Then, each of the supports was immersed into a mixed aqueous solution which contains not only a nitrate of alkali metals but also a nitrate of rare-earth elements in predetermined concentrations. Each of the mixed aqueous solutions was prepared by mixing the nitrate of alkali metals and the nitrate of rare-earth elements with water so as to load the alkali metal ingredient and the rare-earth element ingredient in loading amounts set forth in Table 3 below. Each of the supports was then blown to blow away the water droplets in excess. After drying, each of the supports was burned at 600 °C for 1 hour, thereby completing each of the present catalysts designated at No. 51 through No. 64 in Table 3. Third Preferred Embodiments A plurality of honeycomb supports with Pt loaded were prepared in the same manner as described in the "Reference Embodiment I" section. Then, each of the supports was immersed into a mixed aqueous solution which contains not only a nitrate of alkali metals but also a nitrate of transition elements in predetermined concentrations. Each of the mixed aqueous solutions was prepared by mixing the nitrate of alkali metals and the nitrate of transition elements with water so as to load the alkali metal ingredient and the transition element ingredient in loading amounts set forth in Table 4 below. Each of the supports was then blown to blow away the water droplets in excess. After drying, each of the supports was burned at 600 °C for 1 hour, thereby completing each of the present catalysts designated at No. 65 through No. 76 in Table 4. First Comparative Examples First Comparative Examples, e.g., comparative catalysts designated at No. 42 through No. 50 in Tables 2, 3, and 4, were prepared in the same manner as described in the "First, Second and Third Preferred Embodiments" sections except that each of the honeycomb supports with Pt or Pd loaded was immersed into an aqueous solution which contains one and only nitrate of alkali metals, thereby loading one and only alkali metal ingredient thereon. Examination for Purifying Performance Each of the present catalysts and the comparative catalysts was disposed in an exhaust line of an actual vehicle equipped with a lean burn engine. The lean burn engine had a displacement of 1.6 liters. The vehicle was driven in the urban area running mode, for instance, it was alternately driven in the 10-mode for a certain period of time and then in the 15-mode for another certain period of time, thereby examining the present and comparative catalysts for the conversion of CO, HC and NO x . The results of the evaluation were summarized in the columns designated at "Initial Conversion" in Tables 2, 3 and 4. After the aforementioned evaluation, each of the present catalysts and the comparative catalysts was subjected to a bench test on durability which utilized the same type of engine as above. Namely, each of them was disposed in an exhaust line of the engine, and then the engine was run for 100 hours while adjusting the temperature of the exhaust gas introduced into them at 650 °C. After this bench test was over, each of them was again disposed in the exhaust line of the actual vehicle. The vehicle was driven in the same manner as described above, thereby examining the present and comparative catalysts for the conversion of CO, HC and NO x . The results of the evaluation were summarized in the columns designated at "Conversion after Durability Test" in Tables 2,3 and 4. Evaluation It is appreciated from Tables 2, 3 and 4 that the present catalysts with two alkali metal ingredients loaded, the present catalysts with an alkali metal ingredient and a rare-earth element ingredient loaded, and the present catalyst with an alkali metal ingredient and a transition element ingredient loaded were improved in terms of the NO x conversion after the durability test over the comparative catalysts with one and only alkali metal ingredient loaded. Fourth Preferred Embodiments A plurality of honeycomb supports were prepared by coating them with the alumina coating layer in the same manner as described in the "Reference Embodiment I" section. Each of the honeycomb supports with the alumina coating layer formed thereon was immersed into an aqueous platinum dinitrodiammine solution and/or an aqueous palladium nitrate solution, and thereafter it was blown to blow away the water droplets in excess. After the blowing, each of the supports was dried at 250 °C for 3 hours, thereby loading Pt and/or Pd thereon. The loading amounts of Pt and/or Pd are set forth in Table 5 below. Then, each of the supports with Pt and/or Pd loaded was immersed into a mixed aqueous solution which contains two nitrates of alkaline-earth metals in predetermined concentrations. Each of the mixed aqueous solutions was prepared by mixing the two nitrates of alkali metals with water so as to load the two alkaline-earth metals in loading amounts set forth in Table 5 below. The alkaline-earth metals employed were Ba, Mg, Ca and Sr, and they are combined and loaded. Each of the supports was then blown to blow away the water droplets in excess. After drying, each of the supports was burned at 600 °C for 1 hour, thereby completing each of the present catalysts designated at No. 77 through No. 90 in Table 5. Second Comparative Examples Second Comparative Examples, e.g., comparative catalysts designated at No. 91 through No. 94 in Table 5, were prepared in the same manner as described in the "Fourth Preferred Embodiments" section except that each of the honeycomb supports with Pt and/or Pd loaded was immersed into an aqueous solution which contains one and only nitrate of alkaline-earth metals, thereby loading one and only alkaline-earth metal ingredient thereon. Examination for Purifying Performance Each of the present catalysts and the comparative catalysts was disposed in an exhaust line of an actual vehicle equipped with a lean burn engine. The lean burn engine had a displacement of 1.6 liters. The vehicle was driven in the urban area running mode, for instance, it was alternately driven in the 10-mode for a certain period of time and then in the 15-mode for another certain period of time, thereby examining the present and comparative catalysts for the conversion of CO, HC and NO x . The results of the evaluation were summarized in the columns designated at "Initial Conversion" in Table 5. After the aforementioned evaluation, each of the present catalysts and the comparative catalysts was subjected to a bench test on durability which utilized the same type of engine as above. Namely, each of them was disposed in an exhaust line of the engine, and then the engine was run for 100 hours while adjusting the temperature of the exhaust gas introduced into them at 650 °C. After this bench test was over, each of them was again disposed in the exhaust line of the actual vehicle. The vehicle was driven in the same manner as described above, thereby examining the present and comparative catalysts for the conversion of CO, HC and NO x . The results of the evaluation were summarized in the columns designated at "Conversion after Durability Test" in Table 5. Evaluation It is appreciated from Table 5 that the present catalysts with two alkaline-earth metal ingredients loaded were improved in terms of the NO x conversion after the durability test over the comparative catalysts with one and only alkaline-earth metal ingredient loaded. Among the present catalyst, it is apparent that the present catalysts No. 77 through No. 79 on which the combination of Ba and Mg were loaded exhibited distinguished advantageous effects over the other present catalysts. Fifth Preferred Embodiments A plurality of honeycomb supports with Pt and/or Pd loaded were prepared in the same manner as described in the "Reference Embodiment I" section. Then, each of the supports was immersed into a mixed aqueous solution which contains not only a nitrate of alkaline-earth metals but also a nitrate of rare-earth elements in predetermined concentrations. Each of the mixed aqueous solutions was prepared by mixing the nitrate of alkaline-earth metals and the nitrate of rare-earth elements with water so as to load the alkaline-earth metal ingredient and the rare-earth element ingredient in loading amounts set forth in Table 6 below. Each of the supports was then blown to blow away the water droplets in excess. After drying, each of the supports was burned at 600 °C for 1 hour, thereby completing each of the present catalysts designated at No. 95 through No. 111 in Table 6. Third Comparative Examples Third Comparative Examples, e.g., comparative catalysts designated at No. 112 through No. 115 in Table 6 below, were prepared in the same manner as described in the "Fifth Preferred Embodiments" section except that each of the honeycomb supports with Pt or Pd loaded was immersed into an aqueous solution which contains one and only nitrate of alkaline-earth metals, thereby loading one and only alkaline-earth metal ingredient thereon. Examination for Purifying Performance Each of the present catalysts and the comparative catalysts was disposed in an exhaust line of an actual vehicle equipped with a lean burn engine. The lean burn engine had a displacement of 1.6 liters. The vehicle was driven in the urban area running mode, for instance, it was alternately driven in the 10-mode for a certain period of time and then in the 15-mode for another certain period of time, thereby examining the present and comparative catalysts for the conversion of CO, HC and NO x . The results of the evaluation were summarized in the columns designated at "Initial Conversion" in Table 6. After the aforementioned evaluation, each of the present catalysts and the comparative catalysts was subjected to a bench test on durability which utilized the same type of engine as above. Namely, each of them was disposed in an exhaust line of the engine, and then the engine was run for 100 hours while adjusting the temperature of the exhaust gas introduced into them at 650 °C. After this bench test was over, each of them was again disposed in the exhaust line of the actual vehicle. The vehicle was driven in the same manner as described above, thereby examining the present and comparative catalysts for the conversion of CO, HC and NO x . The results of the evaluation were summarized in the columns designated at "Conversion after Durability Test" in Table 6. Evaluation It is appreciated from Table 6 that the present catalysts with an alkaline-earth metal ingredient and a rare-earth element ingredient loaded were improved in terms of the NO x conversion after the durability test over the comparative catalysts with one and only alkaline-earth metal ingredient loaded.

Claims: A process for purifying an exhaust gas from a lean burn engine comprising sulfur oxides, carbon monoxide, hydrocarbons and nitrogen oxides, said process comprising: bringing said exhaust gas from a lean burn engine into contact with an exhaust gas purifying catalyst, the catalyst comprising: a porous support; at least one catalyst ingredient selected from the group consisting of Pt and Pd, and loaded on said porous support; and at least two ingredients selected from the group consisting of alkali metals, and loaded on said porous support in an amount of from 0.05 to 2.0 mole/liter in total, adsorbing nitrogen oxides in said exhaust gas to said at least two ingredients on said porous support under a lean burn atmosphere in which oxidizing concentration are above a stoichiometric point that is required for oxidizing components to be oxidized in said exhaust gas, and chemically decomposing said adsorbed nitrogen oxides to N 2 by a reaction with said at least one catalyst ingredient on said porous support and said hydrocarbons and carbon monoxide in said exhaust gas under a reduction atmosphere to which said lean burn atmosphere is temporarily changed and which is a fuel-rich atmosphere in which oxygen concentration are below said stoichiometric point, wherein said sulfur oxides react with said at least two ingredients to form composite sulfates, said composite sulfates decomposing in oxygen-lean atmospheres to release SO 2 at decomposition temperatures lower than those of the simple sulfates of said at least two ingredients individually, thereby regenerating said at least two ingredients for NO x storage. A process for purifying an exhaust gas from a lean burn engine comprising sulfur oxides, carbon monoxide, hydrocarbons and nitrogen oxides, said process comprising: bringing said exhaust gas from a lean burn engine into contact with an exhaust gas purifying catalyst, the catalyst comprising: a porous support; at least one catalyst ingredient selected from the group consisting of Pt and Pd, and loaded on said porous support; at least one first ingredient selected from the group consisting of alkali metals, and loaded on said porous support in an amount of from 0.05 to 1.0 mole/liter in total; and at least one second ingredient selected from the group consisting of rare-earth elements including La, and loaded on said porous support in an amount of from 0.05 to 1.0 mole/liter in total, adsorbing nitrogen oxides in said exhaust gas to said at least one first ingredient and said at least one second ingredients on said porous support under a lean burn atmosphere in which oxidizing concentrations are above a stoichiometric point that is required for oxidizing components to be oxidized in said exhaust gas, and chemically decomposing said adsorbed nitrogen oxides to N 2 by a reaction with said at least one catalyst ingredient on said porous support and said hydrocarbons and carbon monoxide in said exhaust gas under a reduction atmosphere to which said lean burn atmosphere is temporarily changed and which is a fuel-rich atmosphere in which oxygen concentrations are below said stoichiometric point, wherein said sulfur oxides react with said at least one first ingredient and said at least one second ingredient to form composite sulfates, said composite sulfates decomposing in oxygen-lean atmospheres to release SO 2 at decomposition temperature lower than those of the simple sulfates of said at least one first ingredient and said at least one second ingredient individually, thereby regenerating said at least one first ingredient and said at least one second ingredient for NO x storage. A process for purifying an exhaust gas from a lean burn engine comprising sulfur oxides, carbon monoxide, hydrocarbons and nitrogen oxides, said process comprising: bringing said exhaust gas from a lean burn engine into contact with an exhaust gas purifying catalyst, the catalyst comprising: a porous support; at least one catalyst ingredient selected from the group consisting of Pt and Pd, and loaded on said porous support; at least one first ingredient selected from the group consisting of alkali metals, and loaded on said porous support in an amount of from 0.05 to 1.0 mole/liter in total; and at least one second ingredient selected from the group consisting of Fe, Ni, Co and Mn, and loaded on said porous support in an amount of from 0.05 to 1.0 mole/liter in total, adsorbing nitrogen oxides in said exhaust gas to said at least one first ingredient and said at least one second ingredient on said porous support under a lean burn atmosphere in which oxidizing concentrations are above a stoichiometric point that is required for oxidizing components to be oxidized in said exhaust gas, and chemically decomposing said adsorbed nitrogen oxides to N 2 by a reaction with said at least one catalyst ingredient on said porous support and said hydrocarbons and carbon monoxide in said exhaust gas under a reduction atmosphere to which is a fuel-rich atmosphere in which oxygen concentrations are below said stoichiometric point, wherein said sulfur oxides react with said at least one first ingredient and said at least one second ingredient to form composite sulfates, said composite sulfates decomposing in oxygen-lean atmospheres to release SO 2 at decomposition temperatures lower than those of the simple sulfates of said at least one first ingredient and said at least one second ingredient individually, thereby regenerating said at least one first ingredient and said at least one second ingredient for NO x storage. A process for purifying an exhaust gas from a lean burn engine comprising sulfur oxides, carbon monoxide, hydrocarbons and nitrogen oxides, said process comprising: bringing said exhaust gas from a lean burn engine into contact with an exhaust gas purifying catalyst, the catalyst comprising: a porous support; at least one catalyst ingredient selected from the group consisting of Pt and Pd, and loaded on said porous support; at least two ingredients selected from the group consisting of alkaline-earth metals, and loaded on said porous support in an amount of from 0.1 to 2.0 mole/liter in total, adsorbing nitrogen oxides in said exhaust gas to said at least two ingredients on said porous support under a lean burn atmosphere in which oxidizing concentrations are above a stoichiometric point that is required for oxidizing components to be oxidized in said exhaust gas, and chemically decomposing said adsorbed nitrogen oxides to N 2 by a reaction with said at least one catalyst ingredient on said porous support and said hydrocarbons and carbon monoxide in said exhaust gas under a reduction atmosphere to which said lean burn atmosphere is temporarily changed and which is a fuel-rich atmosphere in which oxygen concentrations are below said stoichiometric point, wherein said sulfur oxides react with said at least two ingredients to form composite sulfates, said composite sulfates decomposing in oxygen-lean atmospheres to release SO 2 at decomposition temperatures lower than those of the simple sulfates of said at least two ingredients individually, thereby regenerating said at least two ingredients for NO x storage. A process for purifying an exhaust gas from a lean burn engine comprising sulfur oxides, carbon monoxide, hydrocarbons and nitrogen oxides, said process comprising: bringing said exhaust gas from a lean burn engine into contact with an exhaust gas purifying catalyst comprising: a porous support; at least one catalyst ingredient selected from the group consisting of Pt and Pd, and loaded on said porous support; at least one first ingredient selected from the group consisting of alkaline-earth metals, and loaded on said porous support in an amount of from 0.05 to 1.0 mole/liter in total; and at least one second ingredient selected from the group consisting of rare-earth elements including La, and loaded on said porous support in an amount of from 0.05 to 1.0 mole/liter in total, adsorbing nitrogen oxides in said exhaust gas to said at least one first ingredient and said at least one second ingredients on said porous support under a lean burn atmosphere in which oxidizing concentrations are above a stoichiometric point that is required for oxidizing components to be oxidized in said exhaust gas, and chemically decomposing said adsorbed nitrogen oxides to N 2 by a reaction with said at least one catalyst ingredient on said porous support and said hydrocarbons and carbon monoxide in said exhaust gas under a reduction atmosphere to which said lean burn atmosphere is temporarily changed and which is a fuel-rich atmosphere in which oxygen concentrations are below said stoichiometric point, wherein said sulfur oxides react with said at least one first ingredient and said at least one second ingredient to form composite sulfates, said composite sulfates decomposing in oxygen-lean atmospheres to release SO 2 at decomposition temperatures lower than those of the simple sulfates of said at least one first ingredient and said at least one second ingredient individually, thereby regenerating said at least one first ingredient and said at least one second ingredient for NO x storage.

Inventors: DOHMAE KAZUHIKO, HAYASHI TAKAHIRO, IGUCHI SATOSHI, KANAZAWA TAKAAKI, KASAHAHA KOICHI, MATSUMOTO SHINICHI, MIYOSHI NAOTO, SAIKI MOTOHISA, SUZUKI TADASHI, TAKESHIMA SHINICHI, TANAKA TOSHIAKI, TANIZAWA TSUNEYUKI, TATEISHI SYUJI, YAMAZAKI KIYOSHI, DOHMAE, KAZUHIKO, HAYASHI, TAKAHIRO, IGUCHI, SATOSHI, KANAZAWA, TAKAAKI, KASAHAHA, KOICHI, MATSUMOTO, SHINICHI, MIYOSHI, NAOTO, SAIKI, MOTOHISA, SUZUKI, TADASHI, TAKESHIMA, SHINICHI, TANAKA, TOSHIAKI, TANIZAWA, TSUNEYUKI, TATEISHI, SYUJI, YAMAZAKI, KIYOSHI, DOHMAE, KAZUHIKO, C/O K.K. TOYOTA CHUO KENKYUSHO, SAIKI, MOTOHISA, C/O K.K. TOYOTA CHUO KENKYUSHO, SUZUKI, TADASHI, C/O K.K. TOYOTA CHUO KENKYUSHO, YAMAZAKI, KIYOSHI, C/O K.K. TOYOTA CHUO KENKYUSHO
Applicants: CATALER IND CO, TOYODA CHUO KENKYUSHO KK, TOYOTA MOTOR CO LTD, CATALER INDUSTRIAL CO., LTD., KABUSHIKI KAISHA TOYOTA CHUO KENKYUSHO, TOYOTA JIDOSHA KABUSHIKI KAISHA
Application year: 1994
Main classification: B01D53
IPC codes: B01J23, B01J37, B01D53